EP3731317B1 - Battery - Google Patents

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Publication number
EP3731317B1
EP3731317B1 EP19184177.4A EP19184177A EP3731317B1 EP 3731317 B1 EP3731317 B1 EP 3731317B1 EP 19184177 A EP19184177 A EP 19184177A EP 3731317 B1 EP3731317 B1 EP 3731317B1
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EP
European Patent Office
Prior art keywords
battery
current collector
layer
electrode plate
conductive layer
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Application number
EP19184177.4A
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German (de)
English (en)
French (fr)
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EP3731317A1 (en
Inventor
Chengdu Liang
Huafeng HUANG
Qisen Huang
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present disclosure relates to the field of batteries and, particularly, relates to a battery.
  • Lithium ion batteries have been widely used in electric vehicles and consumer electronics due to their advantages such as high energy density, high output power, long cycle life, and low environmental pollution.
  • the lithium ion batteries are subjected to abnormal conditions such as extrusion, collision, or puncture, they can easily to catch fire or explode, causing serious problems. Therefore, the safety issue of the lithium ion batteries greatly limits the application and popularization of the lithium ion batteries. Therefore the safety issue of the lithium ion batteries greatly limits the application and popularization of the lithium ion batteries.
  • US 2007/0015061 A1 discloses a method and apparatus for making thin-film batteries having composite multi-layered electrolytes with soft electrolyte between hard electrolyte covering the negative and/or positive electrode, and the resulting batteries.
  • US 2004/0126654 A1 discloses an electrochemical cell laminate, which comprises electrolyte separator, a cathode film and a cathode current collector, a metallic anode film and insulating support film onto which the cathode film and the cathode current collector are coated onto a first surface thereof and a metallic anode film is positioned onto the second surface thereof.
  • the temperature in the battery may rise when an internal short circuit occurs in the battery due to abnormal conditions such as collision, extrusion, or puncture and on the like.
  • alloy having a low melting point is added into the material of a metal current collector. With increasing of the temperature of the battery, the alloy having low-melting point in the current collector begins to melt, thereby resulting in a broken circuit of an electrode plate and cutting off the current. In this way, the safety of the battery is improved.
  • a multilayered current collector is adopted, in which both sides of a resin layer are connected with metal layers to form a composite. When the temperature of the battery reaches a melting point of the material of the resin layer, the resin layer of the current collector melts to damage the electrode plate, thereby cutting off the current and enhancing the safety of the battery.
  • the present disclosure provides a battery, which can improve safety performance while having good rate performance.
  • a battery in a first aspect of the present disclosure, includes a positive electrode plate, a negative electrode plate and an electrolyte.
  • the positive electrode plate includes a positive current collector and a positive active material layer.
  • the negative electrode plate includes a negative current collector and a negative active material layer, and an electrolyte.
  • the positive current collector includes an insulation layer and at least one conductive layer.
  • the insulation layer is used to support the at least one conductive layer.
  • Each of the at least one conductive layer is used to support the positive active material layer and is located above at least one surface of the insulation layer.
  • Each of the at least one conductive layer has a thickness of D2 satisfying: 300 nm ⁇ D2 ⁇ 2 ⁇ m.
  • At least one protective layer is arranged on at least one surface of each of the at least one conductive layer.
  • the negative current collector is a copper foil current collector having a thickness of 1 ⁇ m to 5.9 ⁇ m.
  • the insulation layer of the positive current collector in the battery of the present disclosure is non-conductive, so its resistance is large. This can improve the short circuit resistance of the battery when the short circuit occurs under abnormal conditions, such that the short circuit current can be greatly reduced, and thus the heat generated by the short circuit can be greatly reduced, thereby improving the safety performance of the battery. Meanwhile, the weight energy density of the battery can be increased by replacing the conventional current collector of metal foil with an insulation layer provided with a conductive layer having a smaller thickness.
  • a protective layer is further arranged above the positive current collector in the battery of the present disclosure.
  • the conductive layer can ensure that the current collector can provide electrons to the electrode active material layer, that is, it has the effects of conduction and current collection.
  • the protective layer can further improve the overall mechanical strength of the current collector, further improve the safety performance of the battery, and at the same time effectively prevent the conductive layer from being damaged, oxidized or corroded, etc., and thus significantly improve an operating stability and a service life of the current collector.
  • the positive current collector of the battery according to the present disclosure can improve the safety performance of the battery, its conductivity is inferior to that of the conventional current collector of aluminum foil. Therefore, the present disclosure uses a copper foil current collector having a thickness of 1 ⁇ m to 5.9 ⁇ m as the negative current collector of the battery. Therefore, the rate performance of the battery can be ensured and the negative electrode can be prevented from precipitating lithium.
  • the battery in the present disclosure can not only improve the safety performance of the battery, but also have the good rate performance, and can also improve the weight energy density of the battery.
  • the embodiments of the present disclosure relate to a battery including a positive electrode, a separator, a negative electrode, and an electrolyte.
  • the positive electrode plate includes a positive electrode collector and a positive active material layer.
  • the positive current collector in the battery of the embodiments of the present disclosure will be described in detail below.
  • the positive current collector in the battery of the embodiments of the present disclosure includes an insulation layer and a conductive layer.
  • the insulation layer is used to support the conductive layer and the conductive layer is used to support the positive active material layer and located above at least one surface of the insulation layer.
  • the conductive layer has a thickness of D2 which satisfies: 300 nm ⁇ D2 ⁇ 2 ⁇ m.
  • the conductive layer in the positive current collector used in the embodiments of the present disclosure can meet the requirement that the current collector provides electrons for the electrode active material layer and thus have a function of conducting and collecting current, thereby improving mechanical strength of the current collector as a whole.
  • the conductive layer has a thickness of D2 which satisfies: 300 nm ⁇ D2 ⁇ 2 ⁇ m.
  • the internal resistance of the battery usually includes an ohmic internal resistance of the battery and a polarization internal resistance of the battery.
  • An active material resistance, a current collector resistance, an interface resistance, an electrolyte composition and the like may all have a significant influence on the internal resistance of the battery.
  • the internal resistance of the battery may be greatly reduced due to the occurrence of an internal short circuit. Therefore, increasing the resistance of the current collector can increase the internal resistance of the battery after the short circuit, thereby improving safety performance of the battery.
  • a large current would be instantaneously generated, and a large quantity of heat is generated by the short circuit accordingly.
  • the heat may usually further initiate aluminothermal reaction at the positive current collector made of aluminum foil, which may further cause the battery to fire, explode, etc.
  • the above technical problems are solved by using a special current collector in which an insulation layer is used to support and a conductive layer with a specific thickness is included.
  • the insulation layer is non-conductive, so its resistance is large. This can improve the short circuit resistance of the battery when the short circuit occurs under abnormal conditions, such that the short circuit current can be greatly reduced, and thus the heat generated by the short circuit can be greatly reduced, thereby improving the safety performance of the battery.
  • the specific thickness in the present disclosure can further allow the current collector to have a larger resistance.
  • the conductive layer is made of aluminum, the aluminothermal reaction of the positive current collector can also be significantly reduced, which significantly reduces temperature rise of the battery during the internal short circuit, thereby leading to a good safety performance for the battery.
  • the material of the insulation layer is selected from organic polymer insulation materials.
  • the organic polymer has a lower density and a lighter weight than metal, and therefore the battery can be further allowed to have a higher weight energy density.
  • the conductive layer uses the metal layer having a smaller thickness so that the weight energy density of the battery can be further increased.
  • the insulation layer can well support and protect the conductive layer arranged on the surface thereof, a breakage of the electrode plate, which is common in the conventional current collector, is unlikely to occur.
  • the organic polymer insulation material is selected from a group consisting of polyamide (abbreviated as PA),polyethylene terephthalate (abbreviated as PET), polyimide (abbreviated as PI), and polyethylene (abbreviated as PE), polypropylene (abbreviated as PP), polystyrene (abbreviated as PS), polyvinyl chloride (abbreviated as PVC), acrylonitrile butadiene styrene copolymers (abbreviated as ABS), polybutylene terephthalate (abbreviated as PBT), poly- p -phenylene terephthamide (abbreviated as PPA), epoxy resin, ethylene propylene rubber (abbreviated as PPE), polyformaldehyde (abbreviated as POM), phenol-formaldehyde resin, polytetrafluoroethylene (abbreviated as PTFE), silicone rubber, polyvinylidene fluoride (abbre
  • the insulation layer mainly plays a role of supporting and protecting the conductive layer.
  • the thickness of the insulation layer is D1, and D1 satisfies 1 ⁇ m ⁇ D1 ⁇ 20 ⁇ m. If the insulation layer is too thin, it is likely to be broken during the processing process of the electrode plate or the like. If the insulation layer is too thick, a volume energy density of the battery adopting the current collector can be reduced.
  • An upper limit of the thickness D1 of the insulation layer can be 20 ⁇ m, 15 ⁇ m, 12 ⁇ m, 10 ⁇ m, or 8 ⁇ m, and a lower limit of the thickness D1 of the conductive layer can be 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, or 7 ⁇ m.
  • the thickness D1 of the insulation layer can be in a range consisting of any one upper limit and any one lower limit. Preferably 2 ⁇ m ⁇ D1 ⁇ 10 ⁇ m, and more preferably 2 ⁇ m ⁇ D1 ⁇ 6 ⁇ m.
  • the conductive layer is too thin, although it is beneficial to increase the room temperature thin film resistor R S of the current collector, it is easily damaged during processing process of the electrode plate or the like. If the conductive layer is too thick, it may affect the weight energy density of the battery, and may not be conductive to increasing the room temperature thin film resistor R S of the conductive layer.
  • An upper limit of the thickness D2 of the conductive layer can be 2 ⁇ m, 1.8 ⁇ m, 1.5 ⁇ m, 1.2 ⁇ m, 1 ⁇ m, 900 nm, 800 nm, 700 nm, 600 nm, or 500 nm, and a lower limit of the thickness D2 of the conductive layer can be 300 nm, 350 nm, 400 nm, or 450 nm.
  • the thickness D2 of the conductive layer can be in a range consisting of any one upper limit and any one lower limit. Preferably, 500 nm ⁇ D2 ⁇ 1.5 ⁇ m.
  • the material of the conductive layer is selected from metallic conductive materials, and preferably selected from at least one of aluminum, copper, nickel, titanium, silver, nickel-copper alloy, or aluminum-zirconium alloy.
  • the conductive layer is preferably made of metallic aluminum.
  • the aluminum content in the conventional positive current collector is high, so when a short circuit occurs in the battery under the abnormal conditions, the heat generated at the short circuit point can initiate a violent aluminothermal reaction, thereby generating a large amount of heat and causing the explosion or other accidents of the battery.
  • the battery of the present disclosure since the content of aluminum in the positive current collector is greatly reduced, the aluminothermal reaction can be avoided, thereby significantly improving safety performance of the battery.
  • the conductive layer can be formed on the insulation layer by means of at least one of mechanical rolling, bonding, vapor deposition, and electroless plating.
  • the vapor deposition is preferably physical vapor deposition (PVD).
  • the physical vapor deposition is at least one of evaporation deposition and sputtering deposition.
  • the evaporation deposition is preferably at least one of vacuum evaporation, thermal evaporation deposition, or electron beam evaporation method (EBEM).
  • EBEM electron beam evaporation method
  • the sputtering deposition is preferably magnetron sputtering.
  • the positive current collector further includes a protective layer arranged on at least one surface of the conductive layer.
  • the protective layer can improve the mechanical strength of the conductive layer, further improve the safety performance of the battery, and at the same time effectively prevent the conductive layer from being damaged, oxidized or corroded, etc., and significantly improve an operating stability and a service life of the current collector.
  • the material of the protective layer is selected from metal oxides, and preferably selected from at least one of aluminum oxide, cobalt oxide, chromium oxide, and nickel oxide.
  • the thickness of the protective layer is D3, and D3 satisfies: D3 ⁇ 1/10 D2 and 1 nm ⁇ D3 ⁇ 200 nm, and preferably 10 nm ⁇ D3 ⁇ 50 nm.
  • An upper limit of the thickness D3 of the protective layer can be 200 nm, 180 nm, 150 nm, 120 nm, 100 nm, 80 nm, 60 nm, 55 nm, 50 nm, 45 nm, 40 nm, 30 nm, or 20 nm.
  • a lower limit of the thickness D3 of the protective layer can be 1 nm, 2 nm, 5 nm, 8 nm, 10 nm, 12 nm, 15 nm, or 18 nm.
  • the thickness D3 of the protective layer can be in a range consisting of any one upper limit and any one lower limit. Preferably, 10 nm ⁇ D3 ⁇ 50 nm. If the protective layer is too thin, it is not enough to protect the conductive layer; and if the protective layer is too thick, the weight energy density and volume energy density of the battery can be reduced.
  • D3 satisfies: 1/2000 D2 ⁇ D3 ⁇ 1/10 D2, that is, the thickness of the protective layer is 1/2000 to 1/10 of D2, and more preferably, D3 satisfies: 1/1000 D2 ⁇ D3 ⁇ 1/10 D2.
  • the protective layer can be arranged on the surface of the conductive layer facing away from the insulation layer.
  • the protective layer when it is arranged on the surface of the conductive layer facing away from the insulation layer, i.e., the upper surface of the conductive layer, it may be referred to as an upper protective layer.
  • the thickness of the upper protection layer is D3', and D3' satisfies: D3' ⁇ 1/10 D2 and 1nm ⁇ D3' ⁇ 200nm, i.e., the thickness of the upper protection layer is smaller than or equal to 1/10 of the thickness D2 and is in a range of 1 nm to 200 nm.
  • the upper protective layer When the upper protective layer is made of a metal oxide, the upper protective layer has a large resistance, so such protective layer can further increase the resistance of the positive current collector to some extent, thereby further improving the short circuit resistance of the battery when a short circuit occurs under abnormal conditions and thus improving safety performance of the battery.
  • the upper protective layer can further increase the mechanical strength of the positive current collector.
  • the specific surface area of the metal oxide is larger than that of the metal, such that a bonding force between the protective layer made of the metal oxide material and the conductive layer is stronger, and the protective layer can better protect the conductive layer.
  • the bonding force between the protective layer having a larger specific surface area and the positive active material layer can be further increased. Therefore, compared with the current collector having no protective layer arranged thereon or having the upper protective layer made of metal, the current collector according to the embodiments of the present disclosure can further increase the bonding force with the positive active material layer, thus the overall strength of the battery can be improved.
  • the protective layer can also be arranged on the surface of the conductive layer facing the insulation layer.
  • the protective layer When the protective layer is arranged on the surface of the conductive layer facing the insulation layer, i.e., the lower surface of the conductive layer, it may be referred to as a lower protective layer.
  • the lower protective layer can form a complete support structure to protect the conductive layer, so as to better protect the conductive layer, thereby preventing the conductive layer from being oxidized, corroded or damaged.
  • the mechanical strength of the current collector is further enhanced.
  • the lower protective layer of the metal oxide material has a large resistance, therefore this type of protective layer can further increase the resistance of the positive current collector to some extent, thereby further improving the short circuit resistance when the short circuit occurs in the battery under the abnormal conditions, and improving safety performance of the battery.
  • the specific surface area of the metal oxide is larger, a bonding force between the protective layer made of the metal oxide and the insulation layer is enhanced.
  • the protective layer can increase roughness of the surface of the insulation layer, which has a function of enhancing the bonding force between the conductive layer and the insulation layer, such that the overall strength of the current collector can be enhanced.
  • the thickness of the lower protective layer is D3", and D3" satisfies: D3" ⁇ 1/10 D2 and 1 nm ⁇ D3" ⁇ 200 nm, i.e., the thickness of the lower protective layer is smaller than or equal to 1/10 of the thickness D2 and is in a range of 1 nm to 200 nm.
  • the protective layer can be arranged on the two opposite surfaces of the conductive layer, that is, both the upper protective layer and the lower protective layer are arranged.
  • a proportional relationship between the thickness D3" of the lower protective layer and the thickness D3' of the upper protective layer is: 1/2 D3 ⁇ D3" ⁇ 4/5 D3'. That is, the thickness of the upper protective layer is greater than the thickness of the lower protective layer. If the thickness of the lower protective layer is increased, it has little effect on improving the mechanical strength, safety performance, and the like of the current collector, but it can affect the weight energy density of the battery.
  • the material of the conductive layer is aluminum
  • the thickness of the conductive layer is 500 nm ⁇ D2 ⁇ 1.5 ⁇ m
  • the material of the protection layer is nickel oxide or aluminum oxide
  • the protection layer is arranged on two opposite surfaces of the conductive layer.
  • FIGs. 1 to 4 are structural schematic diagrams of positive current collectors according to embodiments of the present disclosure.
  • the positive current collector 10 includes a positive insulation layer 101 and two positive conductive layers 102 provided above two opposite surfaces of the positive insulation layer 101.
  • a positive protective layer 103 which is also referred as to an upper protective layer, is arranged on a surface of each positive conductive layer 102 facing away from the positive insulation layer 101.
  • the positive current collector 10 includes a positive insulation layer 101 and two positive conductive layers 102 arranged on two opposite surfaces of the positive insulation layer 101.
  • Two positive electrode protective layers 103 are arranged on two opposite surfaces of each positive conductive layer 102.
  • the positive current collector 10 includes a positive insulation layer 101 and a positive conductive layer 102 arranged on one surface of the positive insulation layer 101.
  • a positive protective layer 103 which is also referred as to an upper protective layer, is arranged on a surface of the positive conductive layer 102 facing away from the positive insulation layer 101.
  • the positive current collector 10 includes a positive insulation layer 101 and a positive conductive layer 102 arranged on one surface of the positive insulation layer.
  • Two positive protective layers 103 are arranged on two opposite surfaces of the positive conductive layer 102.
  • FIGs. 5 and 6 are structural schematic diagrams of a positive electrode plate according to embodiments of the present disclosure.
  • the positive electrode plate 1 includes a positive current collector 10 and a positive active material layer 11 formed on a surface of the positive current collector 10.
  • the positive current collector 10 includes a positive insulation layer 101 and one or two positive conductive layers 102 arranged in this order.
  • the positive active material layer includes a positive active material, a binder, and a conductive additive. Since the positive current collector has poorer conductivity than the conventional aluminum foil current collector, it is preferable that the mass percentage of the conductive additive is not smaller than 0.8 wt% based on a total weight of the positive active material layer. This can ensure that the polarization of the positive electrode plate is small such that it has small affection on the high rate performance of the battery. The higher the content of the conductive additive is, the smaller the polarization is and the better the rate performance of the battery will be. However, if the content of the conductive additive is too high, the charge and discharge capacity of the battery can be reduced.
  • the mass percentage of the conductive additive is 0.8 wt% to 2 wt%.
  • the upper limit of adding the conductive additive can be 2 wt%, 1.8 wt%, 1.5 wt%, 1.3 wt%, or 1.2 wt%
  • the lower limit of adding the conductive additive can be 0.8 wt%, 0.9 wt%, 0.95 wt%, 1.0 wt%, or 1.1 wt%.
  • the conductive additive can be selected from common conductive agents for the electrode plate, such as conductive carbon black, graphene, carbon nanotube, KETJEN black, flake graphite, and the like.
  • the negative electrode plate of the battery includes a negative current collector and a negative active material layer.
  • the negative current collector in the battery according to the embodiments of the present disclosure will be described in detail below.
  • the negative current collector of the battery according to the embodiments of the present disclosure uses a copper foil current collector having a thickness of 6 ⁇ m to 12 ⁇ m. In order to further increase the weight energy density of the entire battery, it is preferred to use a copper foil current collector having a thickness of 1.0 ⁇ m to 5.9 ⁇ m. This is because the positive current collector of the battery according to the present disclosure can improve safety performance of the battery, but its conductivity is inferior to that of the conventional aluminum foil current collector. Therefore, this embodiment of the present disclosure uses the copper foil current collector of the specific thickness along with the positive current collector.
  • the negative current collector according to the embodiments of the present disclosure has good conductivity and a polarization of the electrode plate is small, such that the rate performance of the battery can be ensured and the negative electrode can be prevented from precipitating lithium.
  • the negative current collector is a copper foil current collector having a thickness of 2.0 ⁇ m to 5.9 ⁇ m, more preferably a copper foil current collector having a thickness of 3.0 ⁇ m to 5.9 ⁇ m, and even more preferably, a copper foil current collector having a thickness of 4.5 ⁇ m to 5.9 ⁇ m.
  • a copper foil current collector having an elongation at break greater than or equal to 1% it is preferable to use a copper foil current collector having an elongation at break greater than or equal to 1%. If the copper foil current collector has an elongation at break smaller than 1%, it is liable to be cracked or broken during processing and battery operation, thereby affecting the cost and long-term reliability of the battery
  • a copper foil current collector having an elongation at break greater than or equal to 2% may be used. More preferably, a copper foil current collector having an elongation at break greater than or equal to 3% may be used.
  • the copper foil current collector has an elongation at break greater than or equal to 1% both in the MD direction and the TD direction, so that the copper foil current collector has a certain mechanical strength while improving the weight energy density of the battery. It can be ensured that the copper foil has a good processing property during a manufacturing process of the battery. Also, the battery has good electrochemical properties and long-term reliability after the copper foil is applied to the battery.
  • a copper foil current collector having an elongation at break greater than or equal to 2% both in the MD direction and the TD direction is used. More preferably, a copper foil current collector having an elongation at break greater than or equal to 3% both in the MD direction and the TD direction is used.
  • the "length direction (MD direction)" and “width direction (TD direction)” of the copper foil current collector refer to two dimensions of a surface, respectively, in which the length direction refers to a main dimension direction (i.e., a direction having a larger size), and the width direction refers to a secondary dimension direction (i.e., a direction having a smaller size).
  • the length direction is consistent with a coating direction of respective material layers (e.g., the electrode active material layer) during a manufacturing process of an electrode plate, and is also consistent with a winding direction of the electrode plate during a manufacturing process of an electrochemical device (e.g., a battery).
  • the width direction is perpendicular to the length direction.
  • the copper foil current collector may be a current collector made of a metallic copper, or may be a current collector of a copper alloy such as a copper-nickel alloy, a copper-chromium alloy, a copper-zinc alloy, red copper, bronze, or the like.
  • a copper alloy such as a copper-nickel alloy, a copper-chromium alloy, a copper-zinc alloy, red copper, bronze, or the like.
  • the content of the copper element in the copper alloy is 90% by weight or more.
  • the battery of the present disclosure is preferably a negative electrode plate having a following overcurrent capacity: a single piece of the negative electrode plate having a width of 50 mm, and a fusing time of 10 s or more at a current of 10A. This is because when a thin copper foil current collector is used as the current collector, the negative electrode plate is also required to have a certain overcurrent capacity, otherwise it is easy to "blow" during an operation of the battery, thereby affecting the electrochemical performance and normal operation of the battery.
  • the test method for the overcurrent capacity of the negative electrode plate is as follows.
  • the negative electrode plate was cut to a size shown in Fig. 10 , and a current of 10A was applied to observe the fusing time. The shorter the fusing time is, the worse its overcurrent capacity is.
  • the elongation at break of the copper foil current collector is related to defects in the current collector, which are then related to the process of forming the current collector and its composition.
  • an electrolyte is further included.
  • the room temperature conductivity of the electrolyte is 6.0 mS/cm to 9.0 mS/cm, which can further ensure that lithium is not precipitated from the negative electrode.
  • the side reaction can be increased because the adding proportion of certain organic solvent is too large, and it may affect a cycle life of the battery to some extent.
  • the room temperature conductivity of the electrolyte can be adjusted by adjusting the proportion of the cyclic carbonate and the chain carbonate. If the room temperature conductivity is too high, it is needed to increase the addition amount of the cyclic carbonate, which may increase the side reaction. In addition, the room temperature conductivity can also be improved by adding carboxylic acid ester, and it is not limited to this manner.
  • the battery according to the embodiments of the present disclosure can be of a wound type or a laminated type.
  • the battery can also be one of a lithium ion secondary battery, a primary lithium battery, a sodium ion battery, and a magnesium ion battery. However, it is not limited to these batteries.
  • FIG. 7 is a schematic diagram of a one-time nailing experiment of the present disclosure.
  • the drawing merely shows that a nail 4 punctures one layer of positive electrode plate 1, one layer of separator 3 and one layer of negative electrode plate 2 of the battery.
  • the nail 4 penetrates the entire battery in the actual nailing experiment.
  • the entire battery generally includes a plurality of layers of positive electrode plate 1, separator 3, and negative electrode plate 2.
  • the heat generated at the position where the internal short circuit occurs can be completely absorbed by the battery, and the temperature rise of the battery is also very small, such that the damage on the battery caused by the short circuit can be limited to the nailing position, and only a "point break" can be formed without affecting the normal operation of the battery in a short time.
  • An insulation layer having a certain thickness is selected, and a conductive layer having a certain thickness is formed on the surface of the insulation layer by means of vacuum evaporation, mechanical rolling or bonding, and the protective layer is formed by means of vapor deposition, in-situ formation or coating.
  • the vapor deposition is vacuum evaporation
  • the in-situ formation is in-situ passivation
  • the coating is blade coating
  • the conditions of the vacuum evaporation for forming the protective layer are as follows: a sample is placed in a vacuum evaporation chamber after a surface cleaning treatment, a material of the protective layer in the evaporation chamber is melted and evaporated at a high temperature in a range of 1600°C to 2000°C, and the evaporated material of the protective layer passes through a cooling system in the vacuum evaporation chamber and is finally deposited on a surface of the sample, so as to form the protective layer.
  • the conditions of the in-situ passivation are as follows: the conductive layer is placed in a high-temperature oxidizing environment, the temperature is controlled within a range of160°C to 250°C, and the oxygen supply is maintained in the high-temperature environment, and processing time is 30 min, so as to form a protective layer of metal oxide.
  • the conditions of the gravure coating are as follows: a material of the protective layer and NMP are stirred and mixed, then the slurry of the above material of the protective layer (solid material content is 20% to 75%) is coated on a surface of the sample, the thickness of the coating is controlled by a gravure roll, and finally the coating is dried at 100 to 130°C.
  • a copper foil having a thickness of 8 ⁇ m is selected as a negative electrode collector (i.e., negative electrode plate 1#).
  • the positive electrode slurry or the negative electrode slurry is coated on a surface of the current collector by a conventional coating process of battery and dried at 100 °C, so as to obtain a positive electrode plate or negative electrode plate.
  • the mass percentage of the conductive additive is not smaller than 0.8 wt% based on the total weight of the positive active material layer.
  • Positive Electrode Plate 1-1 represents an electrode plate obtained by preparing a corresponding protective layer on Positive Electrode Plate 1, and so on.
  • the current collector of the conventional positive electrode plate is an Al foil having a thickness of 12 ⁇ m, the positive active material layer is a ternary (NCM) material layer of 55 ⁇ m, and the mass percentage of the conductive additive is 1.5 wt%.
  • NCM ternary
  • Negative electrode plate The negative current collector is a Cu foil having a certain thickness, and the negative active material layer is a graphite material layer of 55 ⁇ m.
  • Ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are used as organic solvents (EC: EMC in a volume ratio of 1:10 to 10:1); the electrolyte is LiPF 6 and the concentration of LiPF 6 is 1 mol/L.
  • electrolytes having a room temperature conductivity of 6.5 mS/cm, 7.0 mS/cm, 7.3 mS/cm, 8.0 mS/cm, 8.5 mS/cm, or 9.0 mS/cm are prepared respectively for the preparation of the battery.
  • a positive electrode plate, a PP/PE/PP separator and a negative electrode plate are wound together to form a bare cell by a conventional battery manufacturing process, then the bare cell is placed into a battery case, an electrolyte is injected into the case, followed by sealing, formation, and the like, so as to obtain a lithium ion battery.
  • the standard battery capacity (25 °C, 1C/1C) is 3.2 Ah.
  • Electrode plate No. Positive current collector Positive active material layer Insulation layer Conductive layer Electrode active material layer Content of the conductive agent Material D1 Material D2 Material Thickness Positive electrode plate 1# PI 2 ⁇ m Al 800 nm NCM 55 ⁇ m 1.5 wt% Positive electrode plate 2# PI 5 ⁇ m Al 2 ⁇ m NCM 55 ⁇ m 1.5 wt% Positive electrode plate 3# PI 6 ⁇ m Al 300 nm NCM 55 ⁇ m 1.5 wt% Positive electrode plate 4# PET 5 ⁇ m Al 500 nm LCO 55 ⁇ m 1.3 wt% Positive electrode plate 5# PET 10 ⁇ m Al 1 ⁇ m NCM 55 ⁇ m 1.2 wt% Positive electrode plate 6# PET 8 ⁇ m Ni 1.5 ⁇ m LCO 55 ⁇ m 0.8 wt% Table 2 Electrode plate No.
  • a method for testing cycle life of the lithium ion battery was performed as follows.
  • a lithium ion battery was charged and discharged at 25 °C and 45 °C respectively, that is, it was firstly charged with a current of 1C to a voltage of 4.2V, then discharged with a current of 1C to a voltage of 2.8V, and the discharge capacity after a first cycle was recorded; and the battery was subjected to 1000 cycles of 1C/1C charging-discharging, and the discharge capacity of the battery after a 1000 th cycle was recorded.
  • a capacity retention rate after the 1000 th cycle was obtained by dividing the discharge capacity after the 1000 th cycle by the discharge capacity after the first cycle.
  • a rate experiment was performed for the lithium ion battery.
  • the specific test method was performed as follows.
  • the lithium ion battery was charged and discharged at 25 °C, i.e., the battery was firstly charged with a current of 1C to a voltage of 4.2V, and then was discharged with a current of 1C to a voltage of 2.8V.
  • the discharge capacity after the first cycle was recorded and divided by the discharge capacity at 25 °C with 1C/1C charge-discharge after the first cycle to obtain a 4 C rate performance of the battery.
  • the graph of temperature of Battery 1# and Battery 4# with time is shown in FIG. 8
  • the graph of voltage with time is shown in FIG. 9 .
  • the battery according to the embodiments of the present disclosure has good cycle performance, which is equivalent to the cycle performance of the conventional battery.
  • the current collectors according to the embodiments of the present disclosure do not have any significant adverse effects on the resulting electrode plates and batteries.
  • the battery prepared by the current collector provided with the protective layer can have a further improved capacity retention rate, indicating a better reliability of the battery.
  • the battery according to the embodiments of the present disclosure can have good safety performance. From the results in Table 6 and FIGs. 8 and 9 , the battery temperature of Battery 1 # (conventional battery) at the moment of nailing rose suddenly by hundreds of centigrade degree and the voltage thereof suddenly dropped to zero. This shows that the internal short circuit occurred in the battery at the moment of nailing, a large amount of heat was generated, a thermal runaway and damage of the battery instantly occurred, such that the battery is unable to continue operating. Furthermore, due to the thermal runaway and damage of the battery occurring immediately after the first steel needle punctured into the battery, it is impossible to perform the continuous nailing on this type of battery by using six steel needles.
  • the temperature rise of the battery can basically be controlled under 6°C, the voltages are substantially constant, and the battery can operate normally, no matter in one-time nailing experiment or in six-time continuous nailing experiment.
  • the battery provided with a protective layer made of a metal oxide material can have the better safety performance.
  • the battery according to the embodiments of the present disclosure can greatly reduce the heat generation caused by the short circuit, thereby improving the safety performance of the battery.
  • the damage on the battery caused by the short circuit can be limited to a "point", and thus merely forms a "point break", without affecting the normal operation of the battery in a short time.
  • the conductive additive within the content range of the present disclosure and the electrolyte within the parameters of the present disclosure can achieve good rate performance.
  • the battery according to the embodiments of the present disclosure has good rate performance comparable to a conventional battery.
  • Example 2 a copper foil having a thickness of 1 ⁇ m to 12 ⁇ m is selected as the negative electrode current collector.
  • the positive electrode plates 2-9, the PP/PE/PP separators and the negative electrode plates 1# to 9# in Embodiment 1 were respectively wound into a bare cell, which was then placed into the battery housing. An electrolyte was then injected, followed by sealing and chemical conversion and the like, and finally a lithium ion battery was obtained.
  • the standard battery capacity (25°C, 1C /1C) is 3.2 Ah.
  • a method for testing cycle life of the lithium ion battery was performed as follows.
  • a lithium ion battery was charged and discharged at a temperature of 25°C ⁇ 2°C, that is, it was firstly charged with a current of 1C to a voltage of 4.2V, then discharged with a current of 1C to a voltage of 2.8V, and the discharge capacity after a first cycle was recorded; and the battery was subjected to 1000 cycles of 1C/1C charging-discharging, and the discharge capacity of the battery after a 1000 th cycle was recorded.
  • a capacity retention rate after the 1000 th cycle was obtained by dividing the discharge capacity after the 1000 th cycle by the discharge capacity after the first cycle.
  • the composition of the copper alloy used for the negative electrode plate 5# is 95 wt% of copper and 5 wt% of nickel.
  • the copper foil current collector of the negative electrode plates 2# to 8# is thinner than that of the negative electrode plate 1#, and therefore, the copper foil current collector having the thickness of 1 ⁇ m to 5.9 ⁇ m can meet the requirements of elongation at break (elongation at break ⁇ 1%), so that the copper foil current collector has a certain mechanical strength to ensure good processing property of the copper foil during battery manufacturing.
  • the copper foil current collector of the negative electrode plates 2# to 8# the negative electrode plate 2# and the negative electrode plate 3# have a short fusing time and a poor overcurrent capacity. Therefore, the copper foil current collector having a thickness of 2.0 ⁇ m to 5.9 ⁇ m has a thin thickness, a large elongation at break, a long fusing time, and a good overcurrent capacity.
  • the lithium ion battery formed by the negative electrode plates 2# ⁇ 8# has a weight energy density of 250 wh/kg or higher, and compared to the lithium ion battery formed by the negative electrode plate 1# or the negative electrode plate 9#, it can effectively increase the weight energy density, and as the thickness of the copper foil current collector increases, the cycle stability of the battery is also gradually improved.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)
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EP19184177.4A 2019-04-26 2019-07-03 Battery Active EP3731317B1 (en)

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JP2023503746A (ja) * 2020-06-02 2023-02-01 寧徳時代新能源科技股▲分▼有限公司 電極アセンブリ、ならびにその関連する電池、デバイス、製造方法、および製造装置
CN111785975A (zh) * 2020-07-31 2020-10-16 蜂巢能源科技有限公司 集流体及其制备方法和应用与阴极和锂离子电池
WO2022174369A1 (zh) * 2021-02-18 2022-08-25 宁德新能源科技有限公司 电化学装置及电子装置
KR102405759B1 (ko) * 2021-07-21 2022-06-08 주식회사 테라테크노스 이차전지용 음극재
CN114122404A (zh) * 2021-11-29 2022-03-01 珠海冠宇电池股份有限公司 极片及电化学装置
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CN112133925A (zh) 2020-12-25
CN110931800B (zh) 2020-11-06
EP3731317A1 (en) 2020-10-28
CN110931800A (zh) 2020-03-27
CN112133925B (zh) 2021-10-26
WO2020215781A1 (zh) 2020-10-29
JP2020184497A (ja) 2020-11-12
JP7163436B2 (ja) 2022-10-31
JP2021082612A (ja) 2021-05-27

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